Non-metallizable arylazoaminonaphthalene sulphonamide or sulphonic acid aryl ester dyestuffs



Uted States Patent 3,546,203 NON-METALLIZABLE ARYLAZOAMINONAPH- THALENE SULPHONAMIDE 0R SULPHONIC ACID ARYL ESTER DYESTUFFS Werner Bossard and Hans E. Wegmuller, Riehen, Switzerland, assignors to J. R. Geigy A.G., Basel, Switzerland No Drawing. Application Ser. No. 547,730, May 5, 1966, which is a continuation-in-part of applications Ser. No. 193,306, May 8, 1962, Ser. No. 225,844, Sept. 24, 1962, and Ser. No. 300,640, Aug. 7, 1963, as a continuationin-part of application Ser. No. 193,306, and Ser. No. 433,796, Feb. 18, 1965, as a continuation-in-part of application Ser. No. 225,844. This application June 6, 1967, Ser. No. 663,464 Claims priority, application Switzerland, May 9, 1961, 5,453/61; Mar. 26, 1962, 3,691/62, 3,693/62 Int. Cl. D06p 1/04, 1/08; C09b 29/06 US. Cl. 260-196 8- Claims ABSTRACT OF THE DISCLOSURE Non-metallizable phenylazonaphthalene dyestuffs, free from sulfonic acid and carboxylic acid radicals are described. The dyestutfs are characterized by having (a) in the 1-position of the naphthalene nucleus a nitroor cyano-substituted benzeneazo radical optionally containing further substituents,

(b) in the 2-position of the naphthalene nucleus an unsubstituted amino group, and

(c) in one of the 3-, 4-, 5-, 6-, 7- or 8-positions of the naphthalene nucleus an aminoor substituted aminosulphonyl group, a phenoxy or substituted phenoxy sulphonyl group, a naphthyl-(1)-oxy sulphonyl group, a naphthyl-(2)-oxy sulphonyl group, a pyridyl-(3)-oxy sulphonyl group, a morpholinyl- (l)-sulphonyl group or a piperidyl-(1)-sulphonyl group. The said dyestuffs are suitable for the dyeing of polyesters, and particularly polyethylene glycol terephthalate fibers, the dyeing produced being distinguished by outstanding fastness to sublimation and light.

This application is a divisional application of our application Ser. No. 547,730, now abandoned, filed May 5, 1966 as a continuation-in-part of our applications Ser. No. 193,306 filed on May 8, 1962, now abandoned, Ser. No. 225,844 filed Sept. 24, 1962, now abandoned, Ser. No. 300,640 filed Aug. 7, 1963, and now abandoned as a continuation-in-part of Ser. No. 193,306, and Ser. No. 433,796 filed Feb. 18, 1965, and now abandoned as a continuation-in-part of Ser. No. 225,844, now abandoned.

This invention relates to a new class of dyes which are specifically suited for the dyeing of polyester and particularly for polyethylene glycol terephthalate fibers and to the dyeings on said fibers which are distinguished by outstanding fastness to sublimation and light.

The dyeing of polyethylene glycol terephthalate fibers among which there are such well-known fibers as Dacron, Terylene, Tergal, Diolen, Trivira and Kodel, presents special problems due to the fact that dyed fabrics made from these fibers are usually subjected to a process by which they are permanently pleated. Permanent pleats are ice applied to dyed fabrics of these fibers by pressing the fabric between two steel plates with simultaneous heating to about C. for a brief period. It is, therefore, necessary that the dyeings subjected to this treatment are fast to sublimation at the aforementioned elevated temperature range; otherwise, the pleated edge will be seriously discolored.

Dyeings of the said fibers in orange to violet shades have hitherto often lacked the necessary fastness to sublimation and, frequently, also failed in fastness to light.

It is, therefore, an object of our invention to provide dyestuffs which dye polyethylene glycol terephthalate fibers in orange to violet shades with good to outstanding fastness to light and to sublimation.

We have found that, surprisingly, this object and others which will become apparent in the description of the invention given hereinafter, are attained by the novel metal free monoazo dyestuffs according to a first aspect of the invention, which are difficultly soluble in water and which are of the formula wherein A is one of the following radicals:

(a) The amino group; (b) a substituted amino group having 1 or 2 nitrogen substituents which are, independently of each other, alkyl with from 1 to preferably not more than 10 carbon atoms, hydroxy-lower alkyl groups, lower alkoxy-lower alkyl, lower alkanolyoxylower alkyl, or a substituted amino group wherein one of the bonds of the amino nitrogen is occupied by hydrogen or one of the aforesaid substituents, while another bond is occupied by benzoyloxy-lower alkyl, cycloalkyl with six ring carbon atoms, preferably cyclohexyl, benzyl, phenyl, lower alkyl-phenyl, lower alkoxy-phenyl, chlorophenyl or bromo-phenyl; (c) unsubstituted phenoxy or phenoxy substituted by lower alkyl, phenyl, lower alkoxy, hydroxy-lower alkoxy, phenoxy, lower alkoxy carbonyl, carbamyl, sulfamyl, carbamyl which is N-monoor N,N- di-substituted with lower alkyl, hydroxy-lower alkyl or lower alkoxy-lower alkyl, sulfamyl which is N-monoor N,N-di-substituted with lower alkyl, hydroxy-lower alkyl, or lower alkoxy-lower alkyl, or phenoxy substituted with N,N-di-l0wer alkyl-amino, lower alkanoyl-amino, chlorine or bromine; or (d) naphthy1-(l)-oxy or naphthyl-(2)- oXy; or (e) pyridyl-(3)-oxy, morpholinyl-(l) or piperidyl-(l); and of Y and Y one is an aryl azo radical of the formula wherein B is phenyl, alkylphenyl with an alkyl moiety of 1 to not more than 8 carbon atoms, lower alkoxyphenyl, chlorophenyl, bromophenyl, fluorophenyl, cyanophenyl, nitrophenyl, trimethylfluorophenyl, lower alkanoylphenyl, lower alkoxycarbonyl-phenyl, phenyloXy-carbonylphenyl, benzyloxy-carbonyl-phenyl, lower alkanoyl- 3 amino-phenyl, chloroor bromo-lower alkanoylaminophenyl, naphthyl-(l) or naphthyl-(Z) and also chlorotriazinylamino-phenyl or chloropyrimidylamino-phenyl; and the other Y is a NH lower alkyl-NH, hydroXy-lower alky1NH, lower alkoXy-lower alkyl- NH, phenylNI-I or a lower alkylphenyl-NH- radical, the dyestuffs of Formula Ia being free from water-solubilizing groups that dissociate acid in water.

Lower when used in connectoin with an aliphatic radical means that said radical has from 1-4 carbon atoms.

The dyestulfs of Formula Ia are generally also suited for the dyeing of such other fibers as cellulose acetate fibers, polyamide fibers or polyacrylonitrile and the like synthetic fibers on an industrial scale. Particularly unexpected is the fact that presence of one substituent A SO as defined above, in the dyestuffs according to the invention, decisively improves the fastness to sublimation and, particularly to light, of the dyeings produced by these dyestuffs on polyester fibers.

Their outstanding, specific dyeing properties on polyester fibers and particularly the fastness to sublimation and to light of their dyeings on polyester fibers distinguish them from azo dyes of similar structure which possess an SO H group instead of the group -SO A for such known SO H groups-containing monoazo dyes show practically no affinity to polyester fibers, and also from monoazo dyes of similar solution which have neither SO -A nor SO H substituents, for dyeings, of such dyestuffs on polyester fibers lack fastness to sublimation and light and are therefore not applicable in commercial dyeing of polyester fibers.

The dyestuffs of Formula Ia as well as similar dyestuffs which fall under the formula are obtained by coupling a diazonium compound of the homocyclic or heterocyclic series with a compound of formula which couples in o-position to the primary or to a secondary amino group, the components being so chosen that the dyestuif does not contain any water solubilising groups which dissociate acid in water.

In the Formulae I and II: of Y and Y one Y is an arylazo group having a homocyclic or heterocyclic aryl radical and containing no water solubilising groups which dissociate acid in water, the other Y is the primary or a secondary amino group; A represents a possibly ringsubstituted aryloxy group or an group in which R is hydrogen, a possibly substituted alkyl, cycloalkyl, aralkyl or aryl group, and R is hydrogen, a possibly substituted alkyl, cycloalkyl or aralkyl group, and R and R together with the aminonitrogen atom also form a heterocyclic ring; and of X and X one X is hydrogen or a substituent which can be replaced by the diazo group and the other X is the primary or secondary amino group.

In Z-aminonaphthalene sulphonyl compounds of Formula I, a substituent which can be replaced by the diazo group is a l-sulphonic acid group.

As carbocyclic diazonium compounds, those of the naphthalene and, preferably, of the benzene series are used. Heterocyclic diazonium compounds are principally S-membered, or also 6-membered heterocyclic compounds, in particular those containing nitrogen and possibly fused rings.

As defined, diazonium compounds usable according to the invention should not contain any substituents which dissociate acid in water such as sulphonic acid or carboxylic acid groups. Otherwise their carbocyclic and heterocyclic radicals can be monoor poly-substituted as desired, for example by hydrocarbon groups such as methyl, ethyl, isopropyl, tert. arnyl, cyclohexyl, isooctyl, phenyl, benzyl groups; by ether groups such as methoxy, ethoXy, phenoxy groups; by acylamino groups such as acetylamino, chloroacetylamino, fi-chloropropionylamino, benzoylamino, chlorobenzoylamino groups; by chlorotriazinylamino and chloropyrimidylamino groups, particularly, however, by electrophilic substituents such as the nitro group, the trifiuoromethyl group, the cyano group, halogens such as fluorine, chlorine and bromine, keto groups, ester groups such as the carbomethoxy, carboethoxy, carboxyisopropoxy, carbobutoxy, carbocyclohexyloxy, carbophenyloxy and carbobenzyloxy group.

Preferably diazonium compounds of the benzene series are used which contain at least one electrophilic substituent in the 0- and/or p-position to the diazonium group.

Diazonium compounds usable according to the invention of the carbocyclic or heterocyclic series are derived, for example, from the following amines: l-amino-Z-nitrobenzene, 1 amino 2 nitro-4-methylbenzene, l-amino- Z-nitro 4 methoxy or -4-ethoxybenzene, 1-amino-2- nitro 4 chlorobenzene, 1-amino-2-nitro-4-trifiuoromethylbenzene, 1 amino 4 nitrobenzene, 1 amino- 4 nitro 2 methylbenzene, 1 amino 4 nitro-2- methoxyor -2-ethoxybenzene, 1 amino 4 nitr0-2- chloroor -2 bromobenzene, 1 amino 4 nitro 2- cyanobenzene, l-amino 4 nitro 2,5 dichlorobenzene, l-amino 4 nitro 2,6 dichloroor -2,6 dibromobenzene, 1 amino 4 nitro 3 carboxyethoxyor -3- carboxybutoxybenzene, 1 amino 2,4 dinitrobenzene, 1 amino 2,4 dinitro 6 chlorobenzene, 1-amino-4- carboxyethoxy, or -4-carboxyphenyloxybenzene, l-amino- 2, 4-, -2,5-, or -3,4-dicyanobenzene, 1- or 2-aminonaphthalene, 2 aminothiophene 5 sulphonic acid methyl or ethyl amide, 2 aminothiadiazole, 2 amino 5 nitrothiazole, 2 amino 6 methoxybenzthiazole or 3- aminoindazole.

If X is the primary or a secondary amino group, the l-aminonaphthalene 3 sulphonyl and 1 aminonaphtha- 1ene-4-sulphonyl compounds are used as coupling components.

Preferred coupling components however, are those in which X is hydrogen and X is the primary or a secondary amino group, Examples of a secondary amino group are the methylamino, ethylamino, propylamino, butylamino, cyanoethylamino, hydroxyethylamino, methoxyethylamino, ethoxyethylamino, cyclohexylamino, benzylamino, phenylamino or tolylamino group; advantageously X is the primary amino group.

In 2-aminonapl1thalene sulphonyl compounds, the sulphonyl group -SO A can be in the 3-, 4-, 5-, 6-, 7- or 8-position of the naphthalene nucleus. Those dyestuffs which are produced by coupling diazonium compounds usa ble according to the invention with Z-aminonaphthalene-4-sulphonyl, Z-aminonaphthalene-S-sulphonyl and 2- aminonaphthalene-6-sulphonyl compounds have a surprisingly good affinity to hydrophobic polyester fibres.

The same dyestuffs are obtained by coupling diazonium compounds usable according to the invention with the corresponding Z-aminonaphthalene sulphonyl-l-sulphonic acids.

These coupling components in which SO A is sulphonic acid aryl ester are obtained, for example, by reacting suitable acylaminonaphthalene sulphonic acids such as carbobenzyloxyaminonaphthalene sulphonic acids with phosphorus oxychloride to form the corresponding sulphonic acid chlorides, condensing these with the desired hydroxyaryl compound to form the corresponding aryl ester and removing the acyl group by hydrogenolysis.

The aryloxy group possibly ring-substituted corresponding to A is derived, for example, from hydroxybenzene, from an alkyl, alkoxy, aryloxy, halogen or tert. amino hydroxybenzene or from a hydroxynaphthalene; thus, for example, from 2-, 3- or 4-metl1ylor 2-, 3- or 4-ethyl-lhydroxybenzene or technical mixtures thereof, from 2,4- dimethyl-, 4-tert. butylor 4-isooctyl-l-hydroxybenzene, from 2-, 3-, or 4-chloro-l-hydroxybenzene or from 2 3- or 4-methoxyor 2-, 3-, or 4-ethoxy-1-hydroxybenzene, also from 3-dimethylaminoor 3-diethylamino-1-hydroxybenzene, from 2- or 4-carbomethoxy-, 2- or 4-carboethoxyor 2- or 4-carbobutoxy-l-hydroxybeuzene, from 4-hydroxydiphenyl ether or from 1- or Z-hydroxynaphthalene.

Coupling components usable according to the invention in which -SO A represents sulphonic acid amides are obtained, for example, by reacting suitable acylaminonaphthalene sulphonic acids with phosphorus oxychloride to form the corresponding sulphonic acid chlorides and condensing these with ammonia or with primary or secondary amines and saponification of the acylamide groups.

The amide group corresponding to A can contain primary, secondary or tertiary nitrogen; as nitrogen substituents it can contain, for example, methyl, ethyl, propyl, butyl, cyclohexyl, phenyl, tolyl, benzyl, hydroxyethyl, cyanoethyl, methoxyethyl and methoxypropyl groups in an combination desired. They are derived, for example, from amines such as ammonia, monolkylamines such as methylamine, ethylamine, propylamine, isopropylamine, n-, secor tert. butylamine, octylamine or decylamine, hydroxyalkylamines such as B-hydroxyethylamine or 'yhydroxypropylamine, alkoxyalkylamines such as fl-methoxyethylamine or B-ethoxyethylamine, y-methoxypropylamine, 'y-ethoxypropylamine or v-phenoxypropylamine, aralkylamines such as benzylamine, arylamines, e.g. phenylamine or a methyl-, methoxyor ethoxy-phenylamine, also dialkylamines, e.g. dimethylamine, diethylamine, dipropylamine, dibutylamine, di-(B-hydroxyethyD-amine or N-methyl-N-fi-hydroxyethylamine, N-alkyl N aralkylamines such as N-methyl-N-benzylamine or N-alkyl-N-arylamines such as N-methyl-N-phenylamine, N-ethyl-N-phenylamine or N-fl-hydroxyethyl-N-phenylamine or cyclic secondary amines such as piperidine, piperazine or morpholine,

The coupling is advantageously performed in mineral acid to weakly acid aqueous solution, preferably with gradual buffering of the mineral acid for example with alkali metal salts of low fatty acids. If desired, a suitable diazonium compound can also be coupled simultaneously with a mixture of two or more coupling components usable according to the invention or a mixture of two suitable diazo components can be simultaneously coupled With H6 or more coupling components usable according to the invention.

A modification of the process for the production of azo dyestufis according to the invention of Formula I wherein of Y and Y one Y is an arylazo group having a homocyclic or heterocyclic aryl radical and containing no water solubilising groups which dissociate acid in water, the other Y is the primary or a secondary amino group; and A is a possibly ring-substituted aryloxy group or a group in which R is hydrogen, a possibly substituted alkyl, cycloalkyl, aralkyl or aryl group and R is hydrogen, a possibly substituted alkyl, cycloalkyl or aralkyl group and R and R together with the aminonitrogen atom also form a heterocyclic ring, consists in reacting an arylazonaphthalene compound of Formula III (III) wherein Y and Y have the meanings given in Formula I and Z represents chlorine or bromine, with a possibly ring-substituted hydroxyaryl compound or with an amine of Formula IV wherein R is hydrogen, a possibly substituted alkyl, cycloalkyl, aralkyl or aryl group; and R is hydrogen or a possibly substituted alkyl, cyclo-alkyl or aralkyl group and R and R together with the aminonitrogen atom also form a heterocyclic ring. The diazo components mentioned in the first process discussed above are also suitable for the second process and the aminonaphthalene sulphonic acids used for the production of starting materials of the general Formula III can be used as coupling components.

The arylazonaphthalene compounds of Formula III usable according to the invention are obtained, for example, by coupling an aryldiazonium compound of the homocyclic or heterocyclic series with an aminonaphthalene sulphonic acid coupling in a position adjacent to a primary or secondary amino group, such as l-aminonaphthalene-3- or -4-sulphonic acid or 2-aminonaphthalene-3-, -4-, -5-, -6-, -7- or 8- sulphonic acid, and converting the azo dyestulf sulphonic acid so obtained into the corresponding sulphonic acid chloride or bromide, for example with a phosphorus chloride or bromide, possibly in the presence of a tertiary nitrogen base.

As examples of possibly ring-substituted hydroxyaryl compounds or their salts, or of ammonia, primary or secondary amines which are to be reacted with the azo dyestuif sulphonic acid chlorides or bromides of Formula 111 are those given in the description of A above.

The sulphonic acid halides of Formula III are condensed with the hydroxyaryl compounds to form arylesters or with the amines of Formula IV to form amides advantageously at raised temperature, possibly in aqueous, organic or in aqueous-organic solution. Suitable organic solvents therefor are those miscible with water, e.g., low aliphatic ketones such as acetone or methylethyl ketone or ether alcohols such as ethylene glycol monomethyl or monoethyl ether, or those not miscible with water, e.g. possibly halogenated aromatic hydrocarbons such as benzene, toluene, xylenes, chlorobenzene, or dichlorobenzenes. The hydroxyaryl compounds to be reacted are used advantageously in the form of their water soluble salts such as the sodium or potassium salts. When amines are used, the reaction is performed advantageously in the presence of an acid binding agent, for example, in an excess of the amine used, or in the presence of an alkali metal salt of carbonic acid such as sodium carbonate.

A preferred group of dyestuffs according to this invention corresponds to the formula wherein one of Y and Y is the primary amino (NH or the secondary amino group and the other Y and Y is the -N=NB group, wherein B is a radical of the benzene or naphthalene series, e.g. naphthyl radical or preferably a substituted phenyl radical; and A is an at most bicyclic carbocyclic aryloxy radical or wherein R is hydrogen, alkyl, especially an alkyl having 1 to 8 carbon atoms, hydroxy(lower)-alkyl, especially fl-hydroxyethyl, (lower) alkoxy(lower)-alkyl, cyclohexyl, benzyl or mononuclear aryl, especially phenyl, methoxyphenyl or methylphenyl, and R is hydrogen, lower alkyl or hydroxy(lower)alkyl, especially fi-hydroxyethyl, and R and R together with the adjacent nitrogen is a sixmembered saturated heterocyclic nucleus, particularly a piperidine, a piperazine or a morpholine nucleus.

If one of Y and Y is a secondary amino group, then it is preferably NH-lower alkyl, e.g. NHCH -NH-C2H5, -NHC3H7, NHC H hydroxy(lower)alkyl, e.g. -NH-CH CH OH, -NH monocyclic aryl, e.g. NHC H or NHC H CH If A in the above formula is an aryloxy radical then it is particularly either an unsubstituted or a substituted 8 monocyclic carbocyclic aryloxy radical, e.g. phenyloxy, chloro-, methyl-, butyl-, octyl-, methoxy-, ethoxy-, phenoxy-, dimethylamino-, diethylamino-, or carbomethoxyphenoxy. If A is a bicyclic carbocyclic aryloxy radical it is preferably an unsubstituted naphthyloxy radical.

In the above formula, the ASO radical can be in either ring of the naphthalene radical, e.g. in the 3-, 4-, 5-, 6-, 7- or 8-position of the naphthalene radical.

In the foregoing when the term lower is used, a total moiety is intended which contains 1 to 4 carbon atoms, e.g. in (lower)alkoxy(lower)alkyl, the total number of carbon atoms is 1 to 4.

Particularly valuable metal-free dyestuffs according to this invention correspond to the formula NII2 wherein B is a radical of the benzene series which is preferably substituted by at least 1 chlorine or bromine atom or at least 1 nitro, cyano, methyl, methoxy, trifluoromethyl, carboethoxy or carbobutoxy group. Advantageously B contains 2 or 3 of these substituents, of which one is nitro or cyano. A therein has the meaning given above.

In addition, dyestuffs in which B in the above formula is the group wherein Y is chlorine, bromine, cyano or nitro and Z is hydrogen, chlorine or bromine, and wherein the said A-SO group is bound in the 5- or 6-position of the naphthalene nucleus, are particularly advantageous.

The dyestuffs according to the invention are suitable for the dyeing of hydrophobic synthetic textile fibers from aqueous dispersion, for example for the dyeing of cellulose dito triacetate, particularly however, for the dyeing of high molecular esters of aromatic polycarboxylic acids and polyfunctional alcohols, e.g. of polyethylene glycol terephthalate such as Terylene, Tergal, or Trevira. The dyestuffs can also be used, however, for the dyeing of synthetic polyamide fibers such as nylon 6 or nylon 66.

Light fast dyeings can also be obtained with the dyestuffs according to the invention on polyacrylonitrile fibers such as, e.g. Orlon.

Polyester fibers are dyed with aqueous dispersions of dyestuffs according to the invention advantageously at temperatures of over under pressure. Very good dyeings are also obtained if polyester fibers are impregnated with concentrated aqueous dispersions of dyestuffs according to the invention, the fabric is squeezed out, dried and then the dyeing is fixed at temperatures of -250. The dyeing can also be performed at the boiling point of the water in the presence of color carriers such as, e.g. phenylphenol, polychlorobenzene compounds or similar auxiliaries.

In some cases the drawing power of the dyestuffs can be further improved by mixing two or more monoazo dyestuffs according to the invention together.

Depending on the composition and mixture of the dyestuffs, orange, red to violet dyeings are obtained on polyester fibers which have very good wet, sublimation and light fastness properties.

The dyestuifs according to the invention are also very well suited for dyeing of polyterephthalate ester fibers blended preferably With cotton, which blended fabrics are subsequently to be subjected to a treatment with hardenable dimethylol urea resins, and finally, after manufacture of apparel therefrom, to a hardening treatment at about 160-l80 C., whereby the apparel is given so-called wash-and-wear properties (Koratron process).

The following non-limitative examples illustrate the invention. Where not otherwise expressly stated, parts are given therein as parts by weight. The temperatures are in degrees centigrade. The relationship of parts by weight to parts by volume is as that of grams to cubic centimeters.

EXAMPLE 1 18.3 parts of 1-amino-2,4-dinitrobenzenes are dissolved in 50 parts of concentrated sulphuric acid and diazotised at 15 with nitrosyl sulphuric acid for 10 hours (corresponding to 6.9 parts of sodium nitrite). The solution of diazonium compound is added dropwise at to a suspension of 29.9 parts of 2-aminonaphthalene-5-sulphonic acid phenyl ester in 900 parts of water, 250 parts of 80% acetic acid and 5 parts of a synthetic dispersing agent. On completion of the coupling, the precipitate formed is filtered oif, washed with water and dried at 60-70" in vacuo. The coupling product is a black-violet powder the composition of which corresponds to the formula.

1 102 SOzO- When milled with an anion active dispersing agent, the dyestuff so obtained dyes polyglycol terephthalate fibers such as Dacron from aqueous dispersion possibly in the presence of carriers, in bordeaux red shades. The bath is substantially exhausted. The dyeings are fast to washing, sublimation and light.

The Z-aminonaphthalene-S-sulphonic acid phenyl ester, M.P. 87-88, used for the coupling is obtained, for example, by reaction of 2-carbobenzyloxyaminonaphthalene- 5-sulphonic acid with phosphorus oxylchloride to form the corresponding sulphonic acid chloride, condensation thereof with phenol to form Z-carbobenzyloxyaminonaphthalene-S-sulphonic acid phenyl ester, M.P. 157-15 8, and hydrogenolysis of the carbobenzyloxy group with hydrogen and palladium on charcoal as catalyst in dioxan.

EXAMPLE 2 A suspension of 17.3 parts of l-amino-4-nitro-2-chlorobenzene in 300 parts of water and 30 parts of 36% hydrochloric acid is diazotised at 0-5 by the dropwise addition of 6.9 parts of sodium nitrite in 50 parts of water. The clear diazonium salt solution is added dropwise at 0-5 to a solution of 32.9 parts of Z-aminonaphthalene- 6-sulphonic acid-(3'-methoxyphenyl)-ester in 1200 parts of water, 200 parts of 80% acetic acid and 2 parts of a non-ionogenic dispersing agent. After some hours, the reaction mixture is buffered to a pH of 44.5 by the addition of sodium acetate.

The dyestuff which precipitates, of the formula l 0 CH3 is filtered oif, washed with water and dried in vacuo at 60-70. The dyestulf is a brown-red powder. A composition produced by milling with a synthetic dispersing agent dyes polyglycol terephthalate fibers such as, eg Terylene or cellulose triacetate fibres, from an aqueous dispersion possibly in the presence of a carrier, in pure red shades. The dyeings are fast to rubbing, sublimation and light.

The coupling component used is obtained from 2-carbobenzyloxyaminonaphthalene-fi-sulphonic acid and 3-methoxyphenol analogously to the method described in Example 1.

If in the above example, instead of the 17.3 parts of 1-amino-4-nitro-2-chlorobenzene, a corresponding amount of the diazo components given in column 2 of the following Tabe I are used and they are coupled under the conditions given in this example with one of the coupling components given in column 3, then dyestuffs are obtained which produce dyeings on polyester fibres having similarly good properties.

TABLE I Shade on polyester N o. Diazo component Coupling component fibres 1 l-amino-Q-nitro- 2-aminonaphthalene4- Red. benzene. suflphonic acid phenyl es er.

2 do Z-aminonaphthalene-S- Reddish su1phonicacid-(3-ethoxyorange. phenyD-estern 3 do 2-aminonaphthalene-6- Do,

sulphom'e acid-(4 tert. butylphenyD-ester.

4 do 2-arninonaphthalene-7- Do.

sulphonic acid phenylester.

5 1-amino4-nltro2- 2-aminonaphtha1ene-3- Red.

ehlorobenzene. sulphonic acid-(4eh1orophenyD-ester.

6 do 2-aminonaphthalene-5- Do.

sulphonic aeid-(3-methylphenyD-ester.

7 do 2-aminonaphthalene-5- Do.

sulphonie acid-(3-dimethylaminophenyl)- ester.

8 ..do 1-aminonaphthalene-3- Do.

sulphonic acid phenylester.

9 do l-aminonaphthalenet- Redsulphonicaoid-(2-methylviolet. phenyl)-ester.

10 1-amino-2,4-di- 2-aminonaphthalene-5- Red.

cyanobenzene. sulphonie aeid-(4-carboxy ethoxyphenyD-ester.

11 do 2-aminonaphthalene-8- Do.

sulphonie aeid-(4-methoxyphenyl)-ester.

12 do Z-methylaminonaphthalene- Redfi-sulphonie acid-(3- violet. methylphenyD-ester.

13 1-amino-4-nitro-2- 2-aminonaphthalene-5- Blueish cyanobenzene. sulphonic acid-(4'-carred.

boxyethoxyphenyD-ester.

14 do 2-aminonaphthalene-5- Do.

sulphonic acid-(3- methoxyphenyl)- 15 do 1-aminonaphthalene-3- Redsulphonic acid-(4 violet. phenoxyphenyD-ester.

16 do 1-aminonaphthalene-4- D0.

sulphonic acid-(3- ch1or0phenyl)-ester.

17 1-arnino-2,4-dinitro 2-aminonaphthalene-4- Violet.

benzene. sulphonic acid phenyl ester.

18 .do 2-methlyaminonaphthalene- Do.

5-sulphonie acid-(4-carboxyethoxyphenyl)-ester.

19 ..do 2-aminonaphthalene-5- Bordeaux sulphonio acid-(4-oetylred.

phenyD-ester.

TABLE ICntinucd TABLE IIContinued Shade on Coupling components or Shade on polyester Diazo mixture of coupling polyester N o. Diazo component Coupling component fibres No. component components fibres 20 1-amino-2,4dinitro 2-aminonaphthalene5- Bordeaux 5 6 l-amino-4-nitro- 2-aminonaphthalene-7-sul- Scarlet benzene. sulphonic acid-(4'- red. benzene phonic acid cyclohexylmethoxyphenyl)-estcr. amide.

21 "do 2-aminonaphthalene-8- Do. 7 ..do 2-aminonaphthalenc-fi-sul- Do.

Sulphonic acid-(4- phonic acid butylamide; methylphcnyD-ester. 2aminonaphthalene-7- 22 1-amino-4nitro-3- Zaminonaphthalene-d Scarlet. sulphonic acid dimethylcarboxybutoxysulphonic acid-(4- 1 amide. benzene. phenoxyphenyD-ester. J 8 l-fll'l'llllO-Z-ChlOTO-ir 2-am1nonaphthalene-S-sul- Red.

23 do 2aminonaphthalene-6- Do. mtrobcnzenc. phonic acid amide.

sulphonic acid-(4- 9 1-amino-2cyano-4- 2aminonaphthalene-fi-sul- Redchlorophenyl)-ester. nitrobenzene. phonic acid methylviolet.

24 6-methoxy-2-amino- 2-aminonaphthalene-5- Red. amide.

benzthiazole. sulphonic acid-(3- 10 do 2-aminonaphthalene-7-sul- Do.

ethoxyphenylyester. phonic acid-N-methyl-N- 25 "do 2'aminonaphthalene-7- D0. 0 (B-hydroxyethyD-amide.

sulphonic acid-(4- 11 1-am1no-2-nitro-4- 2-ami nonaphthalene-G-sul- Scarlet. methylphenyD-ester. methylbenzene. ionic acid ethylamide.

26 1amino-2-bromo4- 2-methylaminonaphthalene- Red- 12 do 2-aminonaphthalcne-6-sul- Do.

nitrobenzene. 5-sulphonic acid-(2- vi ct. fonic acid methoxypropmethylphenyl) ester. ylamide.

27 .do 2ethylaminonaphthalenc-li Do. 13 1-am1no-2,5di- Z-aminonaphthalene-7-sul- Orange.

sulphonic acld-(3- chlorobenzene. ionic acid dimethylamide. methylphenyD-ester. 14 ..do 2-a1ninonaphtha1cne-6-su1- Do.

tonic acid benzylamide. EXAMPLE 3 15 l-amino-tcerboxy- 2-aminonaphthalene-6-sul- Do.

ethoxybenzene. ionic acid propylamidc. A fine suspension of 13.8 parts of 1-amino-2-m'tro-ben- 16 zone in 220 parts of water and 26 parts of 36% hvdroamide. d

' 17 l-amino-2 5di- 2-aminonaphthalene-6'sul- Rc 1on0 18 dlazotlsed m the ilsual at 5 7 by methoxyi-nitroionic acid piperidide. violct.

the addition of 6.9 parts of sodium nitrlte. The clear benzene.

o 18 1-amiuo-2,6-di- 2-aminonaphthalene-G-sul- Red. niazonium salt solution is poured at 0 5 into a dispersion chlomdknitw mm acid diethylamidei of 23.6 parts of 2-am1nonaphthalene-6-sulphon1c ac1d bgnzene 19 l-amino-2,4-di 2-aminonaphthalene-G-sul- Do. methylamlde m 1500 parts of water, 25 parts of 36% 3O cyanobenzenei tonic acid methy1amide hydrochloric acid and 5 parts of an ethylene oxlde-fatty 2o .410 2-aminonaphthalene-G-sul- Do. alcohol condensation product. The reaction mixture is g lgg cyclohexyl' then buffered with sodium acetate to a pH of 4 to 4.5 21 2-amino-5fisullfithyl- Zaminonaghthalfncflisul- Violet.

amidot iop ene. onic aci buty amit e. The dyestufi Whlch preclpltates of the formula 22 2-aminothiadiazole 2-aminonaphthalene-G-sul- Orange.

NH2 ionic acid dimcthylamide.

23 3-amiuoindiazole Z-aminonaphthalene-fi-sul- Do.

ionic acid methylamide. 24 1aminonaphthal- 2-9.minonaphthalene-G-sul- Scarlet.

ene. fonic acid amide. 25 2-aminonaphthal- 2-aminonaphthalene-6-sul- Orange. N02 one. fonic acid methylamide.

| SOzNHCHa EXAMPLE 4 is filtered off, washed, dried in vacuoat 60 and milled with an alkyl-aryl benzene sulphonate. It is a red powder suspenslfm 0f Parts which dyes acetate silk or polyester fibres the latter posnltfobenZeIle In 300 Parts of Water and 30 Parts Of 36% I u I a n I O sibly wlth the addition of carriers, 1n scarlet red shades hydfochloflc 301d 18 dlaZOtlZed at y the dFOPWISe from an aqueous dispersion. The dyeings have very good fastness to washing, sublimation and light.

If, in the above example, instead of the 13.8 parts of l-amino-Z-nitrobenzene, a corresponding amount of the diazo components given in column 2 of the following Table II is used and these are coupled under the same conditions with a coupling component given in column 3, then dyestufis are obtained which produce dyeings on polyester fibres having the same good properties.

addition of a solution of 6.9 parts of sodium nitrite in 50 parts of Water. The clear diazonium salt solution is added dropwise at 05 to a mixture of 11.1 parts of 2- aminonaphthalene-5-sulfonic acid amide and 11.8 parts of Z-aminonaphthalene-S-sulfonic acid methylamide in 1400 parts of water, 100 parts of alcohol and 40 parts of 36% hydrochloric acid. After one hour, the reaction mixture is buffered with sodium acetate to a pH of 4 to 4.5. The red-violet coupling products of the composition SO2NH2 ll S02NHCH3 are filtered 01f, washed neutral with dilute sodium carbonate solution and then washed free of salt with water. The dyestuff mixture is dried at under reduced pressure and then milled with a synthetic dispersing agent.

From aqueous dispersion, the mixture of the two dyestuffs dyes polyester fibres or triacetyl cellulose fibres, possibly with the addition of carriers, in blueish red shades. The dyeings possess a high degree of washing, perspiration, sublimation and light fastness properties.

Similar dyestuffs having the same good properties are obtained if equivalent amounts of the diazo components given in column 2 of the following Table III are coupled under the conditions described in the above example with corresponding amounts of the coupling components given in column 3.

TABLE III Shade on polyester N o. Diazo component Coupling components or mixtures of coupling components fibres 1 1-amino-2-nitrobenzene 2-aminonaphthalene-5-sulphonic acid amide Scarlet. 2 1-amino-4-nitrobenzene 2-aminonaphthalene-5-sulphonic acid propylamide. Do. 3-.." l-amino-il-chloro-i-nitrobenzenc YFaminonaphthalene-Ssulphmic acid methoxyethylamid Red. 4 dn 2-aminonaphthalene-5-sulphomc acid-N-methyl-N-( B-hydrox Do. 5 do 2aminonaphthalene-8-sulphonie acid-N-( B-hydroxyethyD-amide Do. 6 1-amino-2-cyano-4-nitrobenzene. Z-aminonaphthalene-fi-sulphouic acid dibutylamide Red-violet. 7 do 2-am1nonaphthalene-5-sulphon1c acid piperidide Do. 8 l-amino-Q-nitroA-methylbenzene 2-amiuonaphthalene-5-sulphonic acid amide Scarlet.

dn 2-aminonaphthalene-5-sulphonic acid methylamide; Z-aminonaphthalene -sulphonic acid Do.

dimethylamide.

10 1-agnino-2-nitro-Ltrifluoromethyl- 2-aminonaphthalene-S-sulphonic acid dimethylamide Do.

enzene. 11 1-amino-2-nitro-4-methoxybenzene 2-aminonaphthalene-5-su1phonic acid benzylamide Do. 12.- do Z-aminonaphthalene-5-sulphonic acid morpholide D o, 13 -do Z-aminonaphthalene sulphonic acid methoxypropylamide. D0, 14 o-4-carboxyphenyloxy- 2aminonaphthalene-5-sulphonic acid benzylamide Do.

benzene. 15 do Zaminonaphthalene-5-sulphonic acid-N-phenyl-N-methylamide Do. 16"-.. 1-amin0-2-6-dichloro-4-nitro- Z-aminonaphthalene-fi-sulphonic acid methylamidp 3 benzene.

17 do Z-aminonaphthalene-5-sulphonic acid-N-( B-hydroxyethyl)-amidc D0. 18-- Zaminothiadiazole. Z-aminonaphthalene-fi-sulphonic acid cyclohexylamide Orange. 19 do 2-aminonaphthalene-5-sulphonic acid phenylamide D 20 l-aminonaphthalene 2-amin0naphthalene-fisnlphonic acid blltylamide scarlet 21 2-aminonaphthalene 2-aminonaphthalene-5-sulphonic acid dimethylamlde 22, 1-amino-2-nitrobenzene Z-aminonaphthalcne-fi-sulphonic acid-benzylamide. Scarlet, 23 do 2-aminonaphthalene-fi-sulphonic acid-N-fl-hydroxyethylam1de D 24 l-amino-Z-nitrobenzene. 2-amiuonaphthalene-5-sulphonic acid-dibutylamine D 25 1-amino-4-nitrobe11zene Z-aminonaphthalene-fi-sulphonic acid-butylamide D 25 2-aminonaphthalene-5-sulphonie acid-methylamide. Do.

2-aminonaphthalene-5-sulphonic acid-ethylamide Red. 2-aminonaphthaleneS-sulphonic acid-N-flfl di-(hydroxyethyD-armde. Do. 2-aminonaphthalene-5-sulphonic acid methylamide Do. Z-aminonaphthalene-fi-sulphonic acid-N-phenyl-N-methylamide Do. 31 do 2a naphtha1ene-5-su1phonic acid-amide; 2-aminonaphthalene-5-sulphonic acid-butylann e. 32 do Z-aminonaphthalene-S-sulphonic acid-amide; -2-aminonaphthalene-5-su1phonic acid-A-meth- Do.

oxypropylamide. 33 do 2-aminonaphthalene-5-sulphonic acid-octylamide Do, 34 l-am'mo-2-bromo-4-nitrobenze11e- 2-aminonaphthalene-5-sulphonic acid-ethylamide Do, 35.l l-amino-Z-bromo--nitrobenzene- 2-aminona1phthaene-5-sulphonic acid-amide; 2-aminonaphthalene-5-sulphonic acid-A-meth- Do.

oxyprop yaml e. 36 do 2-aminonaphthalene-5-sulphonic acid-octylamide Do, 37 l-amino-2-bromo-4-nitrobenzene Z-aminonaphthalene-fi-N-B-hydroxy-ethylamide 0,

1-amin0-2-cyano-4mitrobenzene 2-aminonaphthalene-fi-sulphonic acid-y-methoxy proplyamide Ruby,

.do Z-amigonaphthalene-sulphonic acid-butylamide; 2-aminonaphthalene-5-sulphonic acid- Do.

am e. 40 do Z-amhonaphthaXene-E-sulphon.ic acid-amide; Z-aminonaphthalene-5-su1phonic aoid-diethyl- D0.

am e. 41 do Z-aminonaphthalene-fisulphonic acid-methylamide; Z-aminonaphthalene-5-sulphonic acid- D0.

2-methoxy-phenylam1de. d 2-aminonaphthalene-5-sulphonic acid-2-methoxy-phenylamide Do.

l-amino- 2-aminonaphthalene-fi-sulphonic acid-butylamide Bordeaux.

d 2-aminonaphthalene-fi-sulphonic acid-N-B-hydroxyethyl Do. do Z-aminonaphthaJene-5-sulphonic acid- -rnethypropylamide, Do. do 2-amiuonaphthalene-5-sulphonic acid-2-rnethoxyphenylamide Do. i 2-aminonaphthalene-5-sulionic acid-methylamide Do. benzene. 42 d0 2-amlnonaphthalene-fi-sulfonic acid-ethylamide; 2-aminonaphthalene-5-sulionic acid-N-B- Do.

hydroxethylamide. 49 1-amino-2,5-dich1or0-4-nitro 2-aminonaphthalene-5-su1iomc acid-methylamide Red.

benzene. 50 do 2-aminonaphthalene-5-sulfonic acid-amide. D 51 1-amino-2-ch10ro-4-nitrobenzenc; Z-aminonaphthalene-fi-sulfomc acld-butylannde D0.

l-amino-2-bromo-4-nitrobenzene. 52 1-amin0-2,4-dinitro-6-ch10ro- 2-aminonaphthalene-8sulfonic acid-v-methoxypropylamide Bordeaux.

benzene. 53 do 2-aminonaphthalene-5-suhonic acid-4methylphenylamide D 54 do Z-aminonaphthaleue-fi-sulfonic acid-morpholide Do.

EXAMPLE 5 A preparation produced by milling with a synthetic (118- 183 parts of 1-amino-2,4-dinitrobenzene are dissolved 55 in 50 parts of concentrated sulphuric acid and the solution is diazotised for 10 hours at 15 with nitrosyl sulphuric acid, corresponding to 6.9 parts of sodium nitrite. The diazonium solution is added dropwise at O5 to a solution of 11.1 parts of Z-aminonaphthalene-S-sulphonic acid amide and 13.9 parts of Z-aminonaphthalene-S-sulphonic acid diethylamide in 50 parts of 30% hydrochloric acid, 40 parts of 80% acetic acid and 800 parts of water. On completion of the coupling, the precipitate formed is filtered oif, washed with water and dried in vacuo at The dyestutf mixture obtained of the formula persing agent dyes polyglycol terephthalate fibres, e.g. Dacron in Bordeaux red shades from an aqueous dispersion, possibly in the presence of a carrier. The dyeings are fast to Washing, rubbing, light and sublimation.

EXAMPLE 6 is a black-violet powder.

methylamide in parts of alcohol, 1400 parts of water l l6 and parts of 36% hydrochloric acid. The dyestuif is a black-brown powder. Dispersed in water with an which precipitates of the formula alkylbenzene sulfonate and with the addition of colour NHZ carriers such as o-phenylphenol, it dyes polyester fibers I CH3 in violet shades. The dyeings have very good fastness to washing, and sublimation.

OzN-N-=N so2N If, 1n the above example, lnstead of the 18.3 parts of I 1-amino-2,4-dinitrobenzene, corresponding amounts of dlazo components given in the followmg Table V are used is filtered off on completion of the coupling, washed neuand y are Coupled Under the condltlofls descrlbei 1H tral and free of salt with water and dried in the usual way. 10 xample 7 with the coupling components given 1n column It is a dark, red-brown powder. After milling with a dis- 3, then dyestuffs are obtained which produce dyeings havpersing agent, violet dyeings which are fast to light and ing the same good properties on polyester fibers.

TABLE IV Shade on polyester No. Diazo component Coupling components or mixtures of coupling components fibres 1 l-amino-2-nitrobenzene 2-aminonaphthalene-4-sulphonic acid methylamide Red.

2,, do 2-aminonaphtha1ene-4-sulphonic acid-N-phenyl-N-methylamide 3 do 2 aminonaphthalene-3-sulphonic acid dimethylamide 4 l-amino-4-nitrobenzene 2-a)mtini)napithalenei-sulphonic acid butylamide; 2 aminonaphthalene4 sulphonic acid diu y aml e.

5 1-amino-2-chloro-4-nitrobenzene 2aminonaphthalene-4-sulphonic acid amide Rediolet.

6 do Z-aminonaphthalene-4-Sulph0nic acid diethylamide Do.

7 1-amino-2-cyano-4-nltrobenzene 2-aminonaphthalene-4-sulphonic acid methylamide Do.

8 1-amino-bnitrM-methylbenzene Zaminonaphthalene-l-sulphonic acid dimethylamide Red.

9 l-amino-Qcarboxyethoxybenzene.. 2-aminonapllthalene-i-sulphonic acid amide Scarlet.

l Z-amino-fi-methoxybenzthiazole- ZaminonaphthalencA-sulphonie acid dimethylamide Red-violet.

11 lamino-Ei-nitrothiazole Z-aminonaphthalene-4-sulphonic acid amide Violet.

12 l-amino- -nitro4methylbenzcne- Z-aminonaphthalene-3-sulphon1c acid-N-flfi-di-(hydroxyethyl)-amlde Scarlet.

2-aminonaphthalene-4-sulphonic acid-N-rnethyl-N-B-hydroxyethylamide Red. 2-2minonaphhalene-t-sulphonic acid-dibutylamide Do. 2-amilriionaphthalene-4-sulphonic acid mcthylamide; Z-aminonaphthale Red-violet.

aim e. 16 l-emino-2-cyano-4-nltrobenzene 2-aminonaphthalene-4-sulphonie acid-y-methoxypropylamide Do. 17 do 2aminonaphthalene-4-sulphonic acid amide; 2aminonaphthaleneA-sulphonie aci Do.

N-Bhydroxyethylamide. 18 1-amino-2,4-dinitrobenzene 2-aminonaphthaleneA-sulphonic acid propylamlde Bordoaax. 19 do 2-arninonaphthalene-4-sulphonic acid ethylamide; 2-amlnonaphthalene-4-sulphonic acld-N- Do.

phenyl-N-mcthylamidc.

TABLE V Shade on polyester N o. Diazo component Coupling components or mixture of coupling components fibres 2-methylaminonephthalene-5-sulphonic acid amide Red.

- Q-methylaminonaphthalene-tisulphonic acid dimethy Do.

Z-(fl-hydroxyethyl)-aminonaphthalene-fi-sulphonic acid-N-ph 2-phenylaminonaphthalene-Eksulphonic acid methylamide 2-butylaminonaphthalene-fi-sulphonic acid dimethylarnid 2-butylaminonaphthaleneA-sulphonic acid methylamide. 2-methylaminonaphthalene-S-sulphonic acid methylamid 8 l-amino-Z-c Z-methylaminonaphthalene-asulphonic acid amide; Z-metliy acid diethylamide. 9 l-amino-2-nitro 4-mcthylbcnzcne 2-(o-tolyl)-aminonaphthaleneh-sulphouie acid cyclohexylamidc Red. 10 do 2-metl1ylaminonaphthalcne-fi-sulphonic acid-N-phenyl-N-methylamide Do. 11 do 2-methylaminonaphthalcue-5-sulionic acid dimethylamide Reddish violet. 1- 1-amine-2,5-diehlorobenzene Z-methylaminonaphthalenc5-sulfonic acid diethylamide Red. 13 do 2-methylaminonaphthalene-5sulfonic acid amide Do. 14 2-amino-fi-methylsulionyl- Z-methylaminonaphthalene-fi-sulionic acid amide Violet benzthiazole.

sublimtation are obtained from an aqueous dispersion EXAMPLE, 8 thereof on polyester fibres such as Tergal of Rhodiaceta, Lyo 18 parts of 2-am1no-6-methoxy-benzthiazole in 100 Dye tuffs having i ila properties ar obtained if parts of concentrated sulphuric acid are diazotised for 3 equivalent amounts of the diazo and coupling components hours at 05 with nitrosyl sulphuric acid, corresponding given in the above Table IV are used under the conto 6.9 parts of sodium nitrite. ditions described in Example 6. The diazonium salt solution is poured while cooling EXAMPLE 7 well into a dispersion of 26.6 parts of l-aminonaphthlene-4-sulfonic acid-N-(B-hydroXyethyD-amide in 1500 parts of water, 30 parts of 36% hydrochloric acid and 5 parts of a synthetic dispersion agent.

The mineral acid is buffered by the addition of sodium acetate. The coupling is completed by stirring for 14 hours at 0-5. The black-violet reaction product which precipitates is filtered off, washed with a great deal of water and dried in vacuo at After milling with a synthetic dispersing agent, the

18.3 parts of 1-amino-2,4-di-nitro-benzene are diazotised at 15 for 10 hours in 40 parts of 80% sulphuric acid with nitrosyl sulphuric acid, corresponding to 6.9 60 parts of sodium nitrate.

The solution of the diazonium compound is then added dropwise at 0-5 while stirring to a dispersion of 29.2 parts of Z-methylaminonaphthalene-S-sulfonic acid diethylamide in 1400 parts of water, 25 parts of 36% hydrochloric acid and 5 parts of synthetic dispersing agent. The

coupling is completed in the usual way and the product is dyestuff of the formula worked up.

The dyestuif obtained of the constitution S NHz 17 dyes polyester fibres such as Trevira of Farbwerke Hoechst Frankfurt am Main in pure violet shades. The dyeings have excellent water and washing fastness properties.

composition of the compound corresponds to the formula Similar dyestuffs with the same good properties are obtained if equivalent amounts of the diazo components 5 2 C =N given in column 2 of the following Table VI are coupled I under the conditions described in the above example with 01 $0200 the corresponding amounts of the coupling components given in column 3. moms) TABLE VI Shade on polyester N o. Diazo component Coupling components fibres 1 l-amino-Z-nitrobenzene l-aminonaphthalenel-sulphonic acid dimethylamide 2 o 1-aminonaphthalene-3-sulphonic acid diethylann'de" D 3- do enzene l-methylaminonaphthalene-4-sulphonic acid amide 4. amino-2-chloro-4-nitrobenzene l-aininonaphthalene-4-sulphonic acid methy1am1de- 5 1-amino-2-cyano-4-nitrobenzene l-aminonaphthalenet-sulphonic acid dlmethylamide Bordeaux 6 1-amino-4-carboxyethoxybenzene. l-aminonaphthalene-B-sulphonic acid cyclohexylamide Orange 7 1-amino-2,5-dich1orobenzene l-aminonaphthalene-t-sulphonic acid amide Do.

8 2-amino-5-nitro-thiazole l-arninonaphtha1ene-4-sulphonic acid dimethylamide Violet.

EXAMPLE 9 It is a brown red powder. After milling with a condensa- A fine suspension of 17.3 parts of 1-amino-2-chloro-4- nitrobenzene in 220 parts of water and 26- parts of 36% hydrochloric acid is diazotised in the usual way at 5-7 with 6.9 parts of sodium nitrite.

The clear solution of the diazonium salt is added dropwise at 0-5" while stirring to a suspension of 358 parts of 2-aminonaphthalene 5 diethylamidosulphonyl-l-sulphonic acid in 1500 parts of water, 30 parts of 36% hydrochloric acid and 5 parts of an ethylene oxide-fatty alcohol condensation product. The whole is stirred for several hours at 0-5 sodium acetate is added to buffer the hydrochloric acid and stirring is continued to complete the coupling. The violet-red dyestutf which precipitates of the formula NHz SOzN(C2 5)z is filtered oif under suction, washed with a great deal of water and dried in vacuo at 60.

Milled with a synthetic dispersing agent, it dyes terephthalic acid polyester fibres from an aqueous dispersion, possibly with the addition of carriers, in blueish red shades.

The dyeings have very good fastness to washing, sublimation and light. The coupling component is obtained, for example by reacting sulphuric acid monohydrate with 2-aminonaphthalene-5-sulphonic acid diethylamide in the cold.

If, in the above example, the 35.8 parts of 2-aminonaphthalene5-diethylamidosulphonyl l sulphonic acid are replaced by 31.6 parts of 2 aminonaphthalene-S- methylamidosulphonyl-l-sulphonic acid or by 33.0 parts of Z-aminonaphthalene 6 dimethylamidosulphonyl-lsulphonic acid and the coupling is performed under the conditions described in the above example, then dyestuffs are obtained which produce red dyeings on polyester fibres which have the same good properties.

EXAMPLE 10 12 parts of 1 (2'-chloro-4' nitrophenylazo)-2-aminonaphthalene-S-sulphonic acid chloride and 8 parts of the sodium salt of 3-diethyla'minophenol in 100 parts of toluene are heated for 4 hours at 80-90". After cooling the reaction mixture, the precipitated dyestufi is filtered 01f, washed with water and dried in vacuo at 60 70". The

tion product of naphthalene sulphonic acids with formaldehyde, the dyestuff so obtained dyes polyglycol terephthalate fibres such as Dacron in pure red shades from an aqueous dispersion, possibly in the presence of carriers. The dyeings are fast to rubbing, light and sublimation.

The l-(2-ch1oro-4' nitrophenylazo)-2-naphthalene-5- sulphonic acid chloride used as starting material is obtained by coupling diazotised 1-amino-2-chloro-4-nitrobenzene with Z-aminonaphthalene-S-sulphonic acid and reacting the dyestuif sulphonic acid with phosphorus oxychloride in chlorobenzene, in the presence of a tertiary nitrogen base.

EXAMPLE 11 15 parts of 1 (2'-cyano-4'-nitrophenylazo)-2-aminonaphthalene-S-sulphonic acid chloride and 8 parts of 3- methoxyphenol and 8 parts of sodium carbonate in 75 parts of acetone and parts of water are heated for 3 hours at 6570. After cooling, 300*parts of water are added to the reaction mixture. The dark precipitate formed is filtered off under suction, washed with water and dried in vacuo at 60-70. The dyestutf is a black-brown powder. Its composition corresponds to the formula NHa l ON -s o20- OCHs The compound is identical with the dyestuif obtained according to Example 2, Table 1, No. 14. A dye preparation milled with a synthetic dispersing agent which contains the dyestutf in finely dispersed form dyes polyglycol terephthalate fibres, e.g. Terylene from aqueous dispersion, possibly in the presence of carriers, in pure blueish red shades. The dyeings are fast to washing, rubbing, sublimation and light. I

The 1-(2'-cyano-4'-nitrophenylazo)-2-aminonapthalene- 5-sulphonic acid chloride used as starting material is obtained by coupling diazotised l amino-4-mtro-2-cyanobenzene with 2-aminonaphthalene-S-sulphonic acid and reacting the dyestuif sulphonic acid with phosphorus oxychloride in chlorobenzene, in the presence of a tertiary nitrogen base.

If in the above example instead of the 15 parts of 1-(2- cyano-4'-nitrophenylazo) 2 aminonaphthalene-S-sulphonic acid chloride, corresponding amounts of the sulphonic acid chlorides given in the following Table VII are used and they are condensed under the conditions described in the example with one of the hydroxyaryl comon polyester fibres.

pounds given in column 3, then dyestufis are obtained which produce dyeings having similarly good properties TABLE VII Shade on polyester No. Sulphonlc acid chloride Hydroxyaryl compound fibre 1 IIIHZ 4-methy1-1-hydroxybenzene Red-orange.

| N O a 2 Same as above. 4-hydroxydiphenyl ether Do.

3 ('31 N H2 4-ch1oro-1-hydroxybenzene Bordeaux.

I N O 2 I S O 201 4 IYTH; 3-methoxy-1-hydr0xy henvene Scarlet.

I CH3 l S O 201 5 NHz Mixture of 2-methyl-l-hydroxybenzene and Mnethyl-l-hydroxy- Red.

| benzene.

6 Same as above B-methoxy-l-hydroxybenzene Do.

7 11TH: 4-tert. butyl-l-hydroxybenzene Blueish red I ON S 0201 8 1TH; 4-dimethylamino-l-hydroxybenzene Scarlet.

W NZM CrHgOOC S 0201 9 IYTHZ 3-methy1-1-hydroxybenzene Do.

CN- N=N 10 ITIHQ 3-methoxy-1-hydroxybenzone Bordeaux.

N 0 a S O 2 C1 11 171112 Z-methoxy-l-hydmxybenvene Red.-

8N=N- s 0201 12... IIIH: 4-tert. butyI-l-hydroxybenzene-. Do.

CN- N=N- I CN OISO TABLE VII-Continued shlade ton No. Sulphonic acid chloride Hydroxyaryl compound i l ri H 13..." (I31 liizH 8'0 201 4-hydroxydipheny1 ether. Bordeaux.

l N O 2 14 BEECH; 4-methyl-l-hydroxybenzene- Red.

S 0 201 15 1TH; 4-dimethylamino-1-hydroxybenzene Do.

OZNQN=N I S O 2 C1 S NHz 16 (EH 0 4-methy1-1-hydroxybenzene- D //CN==N N S O 2C1 17.. O2NO Hydroxybmwnn Bordeaux.

| N 0 2 S O 2 01 I 18. QN=N 3-meth0zy-1-hydroxyb MP Red-orange.

1 1 0 2 S O 2 Cl NHz | 19- OzN-C N=N mixture of aand fl-naphthnl R d,

( 31 S O 2C1 IIIH: 20 O 2NC S 0201 2+lhloro-l-hydroxybenzene Red-violet.

l O N I 21.- O1N-C -N=N S0201 mixture of 2-1'11ethy1-1-l1yd0xy benzene and hydroxybenezne Do.

NHz

l 22. o 2NON=N Z-hydro zymethyl-l-hydroxybenzene Bad.

23. Same as above 3-acety1amino-1-hydroxybenzene Do.

24 do 3-dimethylamino-1-hydroxybenz ene Do.

25. OzN N=N 2-ethoxycarbonyl-l-hydroxybm1ma Bordeaux.

I N O 2 s O 201 26 Same as above l-hydroxy-2-(N-methy1carbamyl)-benzene Do.

TABLE VII Continued Shade on polyester No. sulphonic acid chloride Hydroxyaryl compound fibre 7 27....- O2NON=N Z-hydroxymethyl-l-hydroxybenzeue Do.

SOzCl EXAMPLE 12 ample 4, Table III No. 4. The dyestulf is a dark red 12 parts of 1-(2,4-dinitrophenylazo)-2-aminonaphthalene-6-sulphonic acid chloride, 8 parts of p-tert. butylphenol and 8 parts of sodium carbonate in 50 parts of ethylene glycol monoethyl ether and 75 parts of water are heated for 2 hours at 75-85 After cooling, 400 parts of water are added to the reaction mixture. The dyestuff which precipitates, the composition of which corresponds to the formula I solo-GAMES):

EXAMPLE 13 parts of 1-(2'-ch1oro-4'-nitrophenylazo)-2-aminophthalene-S-sulphonic acid chloride and 5 parts of N- methyl-N-(B-hydroxyethyl)-amine in 40 parts of water are heated for 2 hours at 70-80". After cooling, the reaction mixture is diluted with 200 parts of water. The dyestuii of the formula CHzCHzOH which can easily be filtered is filtered ofl, washed with water and dried in vacuo at 60-70. The compound obtained is identical with the coupling product given in EX- powder. A preparation produced by milling the dyestuff with a synthetic dispersing agent dyes polyglycol terephthalate fibres such as Terylene in pure red shades from aqueous dispersion, possibly with the addition of a carrier. The dyeings are fast to washing, rubbing, light and sublimation.

The 1 (2' chloro 4 nitrophenylazo)-Z-aminonaphthalene-S-sulphonie acid chloride used as starting material is obtained by coupling diazotised 1-amino-2-chloro- 4-nitrobenzene with Z-aminonaphthalene-5-sulphonic acid and reacting the dyestufi? sulphonic acid with phosphorus oxychloride in chlorobenzene, in the presence of a tertiary nitrogen base.

EXAMPLE 14 12 parts of 1-(2'-nitrophenylazo)-2-aminonaphthalene- '6-sulphonic acid chloride and 8 parts of butylamine are heated for 4 hours at 65 in parts of acetone and 50 parts of water. After cooling, 250 parts of water are added to the reaction mixture. The dyestutf which precipitates is filtered off, washed with water and dried in the usual Way. It is a yellow-brown powder. The composition of the compound so obtained corresponds to the formula NHz SIO2NH CHzCHzCHzCHa The dyestufi milled with an alkylbenzene sulphonate dyes polyglycol terephthalate or cellulose triacetate fibres from aqueous dispersion in scarlet red shades which are fast to light and sublimation.

The 1 (2' nitrophenylazo) 2-arninonaphthalene-6- sulphonic acid chloride used as starting material is obtained by coupling diazotised l-amino-Z-nitrobenzene with 2-aminonaphthalene-6-sulphonic acid and reacting the dyestuif sulphonic acid with phosphorous oxychloride in chlorobenzene, in the presence of a tertiary nirtogen base.

Dyestuffs having similar properties are obtained if equivalent amounts of the sulphonic acid chlorides given in column 2 of the following Table VIII are condensed under the conditions described in the above example with corresponding amounts of the amines given in column 3.

TABLE VIII Shade on polyester No. sulphonic acid chloride Amine fibres r 1 CH3-C N=N- @uncm Scarlet.

t 2 OzN-C -N=N H2NCH2OH2CHzOCH Bordeaux.

3 Same as above HzN-octyl D0.

TABLE VIIICntinued Shade on polyester No. Sulphonic acid chloride Amine fibres 14 ozN -N=N HzN-CHgCHzOH Red.

I S Oral 1 GHzCHzOH OzN- N=N- NI-I\ Bordeaux red.

l S 02(31 F 16 0zN-QN=N- Jim-O Red.

( 31 SO2C1 lH CHr-CH 17 Same as above N /NCH CH OH D0.

CHzCHg EXAMPLE 15 EXAMPLE 18 2 parts of the dyestuif mixture obtained according to Example 5 are dispersed in 4000 parts of water. 12 parts of the sodium salt of o-phenylphenol and 12 parts of diammonium phosphate are added to this dispersion and 100 parts of a polyester fabric are dyed for 1 hours at 9598. The dyeing is rinsed and after-treated with dilute caustic soda lye and a dispersing agent.

A bordeaux dyeing is obtained which is fast to washing, rubbing, light and sublimation.

If in this example, the 100 parts of terephthalic acid polyglycol ester fabric are replaced by 100 parts of cellulose triacetate fabric, dyeing is performed under the conditions given and the dyeing is then rinsed with water, then a. pure bordeaux dyeing is produced which has very good fastness to perspiration, and sublimation.

EXAMPLE 16 2 parts of the dyestuif mixture obtained according to Example 4 in 2000 parts of water which contains 4 parts of a synthetic dispersing agent are finely suspended in a pressure dyeing apparatus. The pH of the dyebath is adjusted to 6 to 6.5 with acetic acid.

100 parts of terephthalic acid polyester fabric are introduced at 50, the temperature is raised within minutes to 140 and dyeing is performed for 50 minutes at this temperature. The dyeing is then rinsed with water, soaped and dried. When these conditions are kept, a blueish red dyeing is obtained which is fast to washing, perspiration, light and sublimation.

The dyestuffs described in the other examples produce dyeings of equal quality when used according to this process.

EXAMPLE 17 3 parts of the dyestuff obtained according to Example 11 are dispersed in 4000 parts of water. 25 parts of the sodium salt of o-phenylphenol and 25 parts of diammonium phosphate are added to this dispersion and 100 parts of polyglycol terephthalate yarn are dyed for 1 /2 hours at 9598. The dyeing is rinsed and after-treated with caustic soda lye and a dispersing agent. Under these conditions a pure blueish red dyeing is obtained which has very good fastness to sublimation and light.

Polyglycol terephalate fabric such as Dacron of El. du Pont de Nemours is impregnated in a padding mangle at 40 with an aqueous dispersion composed as follows:

20 parts of the dyestuff mixture obtained according to Example 4, finely dispersed in 7.5 parts of sodium alginate,

20 parts of triethanolamine,

20 parts of a non-inorganic wetting agent and 900 parts of water.

The fabric is squeezed out to increase of its original Weight, dried at 100 and the dye is fixed for 30 seconds at a temperature of 210. The dyed fabric is rinsed with water, soaped and dried. Under these conditions, a blueish red dyeing is obtained which is fast to washing, rubbing, light and sublimation.

The dyestuffs described in the other examples also produce dyeings of equal quality by this process.

EXAMPLE 19 NHz A preparation produced by milling this dyestufl' with an alkali-lignin sulfonate, dyes polyglycol terephthalate In the description of a second aspect of the invention given below, where reference is made to preceding numbers of formulas or examples or symbols used in such formulas, it is to the identified formula, example or symbol in connection with this second aspect of the invention.

According to this second aspect of the invention, it has now been found that new, valuable, metal-free monoazo dyestuffs which are difficulty soluble in water are obtained if a diazonium compound of the benzene series is coupled with a compound of the Formula I them-d wherein X represents hydrogen or a substituent which can be replaced by the diazo group, and R represents an unsubstituted lower alkyl or a monocyclic aryl group, and the components are so chosen that the dyestuffs do not contain any water solubilizing groups which dissociate acid in water, and are free from metallizable substituent groupings in their molecules.

In Z-aminonaphthalene sulfones of Formula I, a 1- sulfonic acid group is employed as substituent X which can be replaced by the diazo group.

As defined, diazonium compounds of the benzene series usable according to the invention should not contain any substituents which dissociate acid in water such as sulfonic acid or carboxylic acid groups. The benzene radicals can otherwise be monoor polysubstituted as desired, for example by hydrocarbon groups such as methyl, ethyl, isopropyl, tert. amyl, cyclohexyl, isooctyl, phenyl, benzyl groups, by ether groups such as methoxy, ethoxy, 2-hydroxy-ethoxy, phenoxy, cresoxy, chlorophenoxy, phenylthio groups; by acylamino groups such as acetylamino, chloroacetylamino, B-chloropropionylamino, methylsulphonylamino, chloromethylsulphonylamino, :benzoylamino, chlorobenzoylamino groups; by chlorotriazinylamino, chloropyrimidylamino groups; in particular, however, by electrophilic substituents such as the nitro group, the trifiuoromethyl group, the cyano group, the halogens fluorine, chlorine and bromine, keto groups, ester groups such as the carbomethoxy, carboethoxy, carboisopropyloxy, carbobutyloxy, carbocyclohexyloxy, carbophenyloxy, carbobenzyloxy group; by sulphonic acid amide groups such as the sulphonic acid dimethylamide, diethylamide, dibutylatnide, cyclohexylamide, phenylethylamide, piperidide, and morpholide group Those diazonium compounds are preferred, which contain at least one electrophilic substituent in the or the p-position to the diazonium group. Dyestuffs which are specially fast to light are obtained from diazonium compounds containing electrophilic substituents in the 0- and p-positions to the diazonium group.

Coupling components usable according to the invention contain the sulphonyl group -SO R in the 3-, 4-, 5-, 6-, 7- or 8-position. When R represents an unsubstituted lower alkyl group, it is e.g. the methyl, ethyl, propyl, iso-propyl, butyl or iso-butyl group; when R represents a monocyclic aryl group it is preferably the phenyl, methylphenyl or chlorophenyl group.

Dyestuffs which are produced by coupling diazonium compounds usable according to the invention with 2- aminonaphthalene-3-sulphones, 2 aminonaphthalene 4- sulphones, 2-aminonaphthalene-S-sulphones and Z-aminonaphthalene-6-sulphones have surprisingly good afiinity to hydrophobic polyester fibers.

The same dyestuffs are obtained by coupling diazonium compounds usable according to the invention with the corresponding Z-aminonaphthalene alkylsulphonyland arylsulphonyl-l-sulphonic acids.

Good dispersibility of dyestuffs according to the invention is attained on the one hand by suitable choice of the diazonium compound and on the other by suitable substitution of the coupling component. Suitable substituents of coupling components according to the invention are, for example, the methylsulphonyl, ethylsulphonyl, propylsulphonyl, ispropylsulphonyl, butylsulphonyl, phenylsulphonyl, and the tolylsulphonyl group.

Aminonaphthalene methylsulphones usable according to the invention are obtained, for example, by reduction of suitable acylaminonaphthalene sulphonic acid chlorides with sodium sulphite to form the corresponding sulphinic acids, condensation of these with chloroacetic acid followed by decarboxylation of the carboxymethylsulphonyl group and simultaneous saponification of the acylamino group. For example, starting from 2-acetylaminonaphthalene-S-sulphonic acid chloride the corresponding 2-aminonaphthalene-5-methyl-sulphone is obtained by this process. It is obtained in good yield and melts at 137-138.

Aminonaphthalene arylsulphones usable according to the invention are obtained, e.g. by careful reaction of corresponding acylaminonaphthalene sulphonic acid chlorides with benzene hydrocarbons in the presence of suitable Lewis acids and subsequent saponification of the acylamino groups.

Thus, for example, 2-aminonaphthalene-S-p-tolylsulphone, M.P. 196-197 is obtained by reaction of Z-acetylaminonaphthalene-5-sulphonic acid chloride with toluene in the presence of aluminium chloride and subsequent saponification of the acetylamino group.

The coupling is performed preferably in mineral acid to weakly acid aqueous solution, advantageously while gradually buffering the mineral acid, e.g. with alkali metal salts of low fatty acids. It is also possible to couple a suitable diazonium compound with a mixture of two or more coupling components usable according to the invention, the coupling being performed simultaneously.

The dyestuffs according to the invention are suitable for the dyeing of hydrophobic synthetic textile fibres from aqueous dispersion, e.g. for the dyeing of cellulose triacetate. They are particularly suitable, however, for the dyeing of high molecular esters of aromatic polycarboxylic acids with polyfunctional alcohols, e.g. glycol terephthalates such as Terylene or Dacron Terga or Trevira. The dyestuffs can also be used for the dyeing of synthetic polyarnide such as nylon or of Perlon.

Polyester fibres are dyed with aqueous dispersions of dyestuffs according to the invention, advantageously at temperatures of over under pressure. Dyeing can also be performed, however, at the boiling point of the water in the presence of colour carriers such as, e.g. phenylphenol, polychlorobenzene compounds or similar auxiliaries.

In isome cases, the drawing power of the dyestuffs can be further improved by mixing two or more of the monoazo dyestuffs according to the invention.

31 Depending on their composition and the mixture of the dyestufls, orange, red to violet dyeings can be attained on polyester fibers which have very good wet fastness as well as very good fastness to sublimation and light. In the broadest aspect of the invention it concerns monoazodyestufis of the formulae V, VI, VII and VIII wherein B is aryl consisting of from one to two sixmembered rings, with maximally 10 ring carbon atoms, and of, as the exclusive substituents, from to 2 of the dispersibility-steering substituents defined below and from 0 to 3 of the shade-influencing substituents defined below; preferably, B is aryl with six ring carbon atoms, and with from 1 to 3 shade-influencing substituents as the exclusive substituents; R is preferably hydrogen, but it can also be alkyl with maximally four carbon atoms, especially methyl or ethyl, further, phenyl, methylphenyl, methoxyphenyl, chlorophenyl or bromophenyl; R in Formulae III and IV is alkyl with maximally four carbon atoms, especially methyl or ethyl; and R in the Formulae V and VI is phenyl, alkylphenyl, wherein alkyl is methyl or ethyl, alkoxyphenyl wherein alkoxy is methoxy or ethoxy, chlorophenyl or bromophenyl.

Particularly valuable monoazodyestufis of the present invention are those of the Formulae IX and X wherein Y is chloro, bromo, cyano or nitro; Z is hydrogen, chloro or bromo; R in Formula VII is alkyl with maximally four carbon atoms, especially methyl or ethyl; and R in Formula VIII is phenyl, alkylphenyl wherein alkyl is methyl or ethyl, alkoxyphenyl wherein alkoxy is methoxy or ethoxy, chlorophenyl or bromophenyl.

The term dispersibility-steering substituents as used in this application stands for the following substituents; alkyl with 1 to 8 carbon atoms, cyclohexyl, benzyl, phenyl, alkoxy having 1 to 4 carbon atoms, and phenoxy substituted in aryl which has six ring carbon atoms, and the following acylamino radicals: acetylamino, chloroacetylamine, p chloropropionylamino, methylsul- 32 fonylamino, chloromethylsulphonylamino, benzoylamino, chlorobenzoylamino, chlorotriazinylamino, chloropyrimidylamino substituted in aryl which has six to ten ring carbon atoms.

The term shade-influencing substituents as used in this application stands for the following substituents: nitro, trifiuoromethyl, cyano, fluoro, bromo, chloro, acetyl, benzoyl, carbalkoxy with maximally 5 carbon atoms, carbocyclohexyloxy, carbophenoxy and carbobenzyloxy substituted in aryl which has six ring carbon atoms, and nitro, cyano, bromo and chloro substituted in aryl which has 10 ring carbon atoms.

Particularly light-fast dyeings are obtained on polyethyleneglycolterephthalate (Terylene) fibres with the aforesaid dyestuffs in which B is phenyl substituted with 2 to 3 light-fastness improving substituents, which are nitro, cyano, bromo and/or chloro. Best results are obtained with the last mentioned dyestuffs in which B has only two light-fastness improving substituents one of which is a nitro group in p-position to the azo bridge.

Terylene fibres dyed with the last mentioned dyestuffs are distinguished by the following advantages: excellent drawing power, fastness to rubbing, fastness to light and fastness to sublimation.

When dyeing polyhexarnethylenediamine adipate, optimal results are obtained with the compounds of Formulae VII and VIII in which the shade-influencing substituents are partially or entirely replaced by one to two of the above mentioned dispersibility-steering substituents.

The following examples illustrate the invention. Where not otherwise expressly stated, parts and percentages are by weight. The temperatures are in degrees centigrade. The relationship of parts by weight to parts by volume is as that of grams to cubic centimeters.

EXAMPLE 20 The diazonium compound of 17.25 parts of 1-amino-2- chloro-4-nitrobenzene is added dropwise at room temperature to a solution of 23.5 parts of Z-aminonaphthalene-6-ethylsulphone and parts of 36% hydrochloric acid in 1500 parts of water and 5 parts of an anion active dispersing agent. The pH of the reaction mixture is then buffered with sodium acetate to 4-4.5. On completion of the coupling, the red precipitate is filtered off under suction, washed with a lot of water and dried at 60-70 in vacuo. The dyestufi so obtained of the formula SOzCzHs is a brown-red powder which, when milled with an alkylarylbenzene sulphonate, dyes polyester fibers such as Dacron in red shades from aqueous dispersion, with or without the addition of carriers. The dyeings have very good fastness to washing and light.

The coupling component used is obtained, for example, by reduction of the Z-acetylaminonaphthalene-6-sulphonic acid chloride with sodium sulphite, alkylation of the sulphinic acid obtained with diethyl sulphate and subsequent saponification of the acetylamino group.

If in the above example, instead of the 17.25 parts of 1-amino-2-chloro-4-nitrobenzene, corresponding amounts of the diazo components given in the following Table IX are used and they are coupled under the conditions given in the above example with one of the coupling components given in column 3, then dyestuffs are obtained which produce polyester dyeing having similarly good properties,

TABLE IX Shade 011 polyester N o. Diazo component Coupling component or mixture of coupling components fibres 1 l-amjno-Z-njtrobenzene 2-aminonaphthalene-fi-methyl su1phone 2 d 2-aminonaphthalene-7-ethyl sulphone- 3 l-arn 2-aminonaphthaleneo-phenyl sulphone 4 do 2-arninonaphthalene-6ethyl sulphone; 2 5 1-amino-2-ohloro-4-nitrohenzene- Z-aminonaphthalene-7-isopropyl su1pl1one Red. f]? 1-a1niino-2-cyano-4-nitrobenzene 2-anginonaphthalene-6-methyl sulphone Bluish-red.

0.-.. o Do. 8 I-aJmjno-2,fi-dichloro--nitro- 2-aminonaphthalene-7-methylsulphone Red.

enzene. 9 o 2-aminonaphthalene-(i-p-tolylsulphone Do. 10 l-amino-2cyano-4-nitrobenzene. Z-aminonaphthalene-6methyl sulphone; Z-aminonaphthalene-(i-ethylsulphone Bluish red. 1 0 2-aminonaphthalene-7-butylsulphone Do. 12 1-amino-2,4-dinitro-6-chlorbenzene 2-aminonaphthalcne-(i-methylsulphone, Bordeaux. 13 l-amino-Z-chloro-4-nitro-henzene 2-aminonaphthalene-7-phenyl-su1phone.. Red. 14-.. 1-amino-2-bromo4-nitro-benzene. Z-aminonaphthalene-7-p-tolyl-sulphone i Do. 15 l-amino-2-chloro-4-nitro-benzene.-- Z-aminonaphthalene-fi-methyl-sulphone Do. 16 1-amino-2,4-dinitro-benzene .do t Bordeaux. 17 "do 2-aminonaphthalene-fiethylsulphone Do.

EXAMPLE 21 25 acid are used and coupling is performed under the condi- 21.75 parts of 1-amino-2,4-dinitro-6-chlorobenzene are tions given. dissolved in 40 parts of concentrated sulphuric acid and EXAMPLE 22 diazotized at 20-25" with nitrosyl sulphuric acid correspending to 6.9 parts of sodium nitrite. The diazonium salt 16.3 parts of 1-am1no-2-cyano-4-nitrobenzene are (.115- solution so obtained is added dropwise at 0-5 to a solusolved in 80 parts of concentrated sulphuric acid and tion of 30.1 parts of 2-amino-S-methylsulphonyl-naphdiazotised at room temperature for 10 hours with nitrosyl thalene-l-sulphonic acid in 200 parts of concentrated sulphuric acid, corresponding to 6.9 parts of sodium n1- sulphuric acid, 1500 parts of water and 5 parts of a fatty trltealcohol polyglycol ether. The black-violet coupling prods llt 0f the dlaZOIllllm Compound 15 added drop net of the for la wise at 0-5 to a solution of 11.05 parts of Z-amino-naph- C1 NHZ thalene-S-methylsulphone and 14.85 parts of Z-aminonaphthalene-5-p-tolylsulphone and 100 parts of 36% hydrochloric acid in 1500 parts of water and 10 parts of a OzN- N N- dispersing agent. After one hour, the pH of the reaction 11102 8020115 40 mixture is buffered to 4-4.5 with sodium acetate.

The violet coupling product mixture obtained of the m o i 1s filtered ofl", washed neutral with dilute sodlum carbonate co P S non NHe NHz (IN 2401011. ON sm-4m solution and finally washed free of salt with water. The dry is filtered oif, washed neutral and free of salt in the usual dyestuff is then milled with a dispersing agent. From an way and finally dried at 70 under reduced pressure. aqueous dispersion this dyestuff preparation dyes polyester The dry dyestuff is milled with an alkylbenzene sulphofibers or cellulose triacetate fibers, with or without the use 60 nate; this dyestuif preparation dyes polyester fibres such of carriers, in bordeaux shades. The dyeings are very as Tergal of Rhodiaceta, Lyons, France, in the presence fast to water, washing and sublimation. The coupling of a carrier in bluish-red shades. The dyeings have very component used is obtained, for example, by reacting good fastness to washing, perspiration, light and sublimasulphuric acid monohydrate with Z-aminonaphthalene-S- tion.

methylsulphone in the cold. 2 -arninonaphthalene-S-methyl- The 2.amin0 naphthelene-5-p tolylsulphone M.P sulPhone 15 Produced, for example by 197, used together with the 2-amino-naphthalene-5- reduction of the 221etylamimmaPhth316m?S'SUIPhOnic methylsulphone as coupling component, is obtained, for acid chloride With sodium sulphite, condensation of the example reacting 2-3cetyl-aminonaphthalene-5-sul sulphinic acid obtained with chloroacetic acid followed by phonic acid chloride h toluene in the presence f alumidecarboxylation of the carboxymethylsulphonyl group hum hl f llow d by if i the acetylamino with simultaneous saponification of the acetylamino group. group A dyestuif having equivalent properties is obtained, if in Dyestuffs having similar properties are obtained if equithe above example, instead of the 30.1 parts of Z-aminomolecular amounts of the diazo and coupling components naphthalene-5-methylsulphonyl- 1 -sulphonic acid, 31.5 given in the following Table X are coupled under the parts of Z-aminonaphthalene-S-ethylsulphonyl-1-sulphonic conditions described in Example 3.

TABLE X Shade on polyester N0. Diazo component Coupling component or mixture of coupling components fibres 1 1-amino-2-nitrobenzeue Z-aminonaphthalene-B-ethylsulphone- Scarlet.

do Z-aminonaphthaleneS-methylsulphone Do. 3. Lamincwi-nitrobenzene Z-aminonaphthalene-5phenylsulphone Do. 4. l-amincz-nitrol-methylbenzene Z-aminonaphthalene-8-p-tolylsulphone..

6. 1-amino-2-chloro-4-nltrobenzene Z-aminonaphthalcne-8-isopr0pylsulphone 6. 1-amino-2nltro-4chlorobenzene 2-aminonaphthalene-fi-butylsulphone 7. d0 2-aminonaphthalene-5-p-toly hone 8 1-amino-2-nitro-4-trifiuoromethyl 2-aminonaphthalene5-methylbenzene benzene. 9 l-amino-Z-methoxyA-nitrobenzene. 2-aminonaphthalene-5-ethylsulphonyl-l-sulphonic acid Scarlet. l-amino-Z-nitrMmethoxybenzene. 2-aminonaphthalene-8-phenylsulphone D0. l-ami11o-2-cyano4-nitrobenzene. 2-aminonaphthalene-S-methylsulphone Red. 12..-" l-abmiIl0-2,6-di(3h10l'0-4-Ditl'0 2-aminonaphthalene-5-ethylsulphnnn Do.

enzene. l'i o 2-aminonaphthalene-5-isopropyl ulnhone D0. 14"-.. 1-amino-2-chloro-4nitrobenzene 2-aminonaphthalene5-p-toly1sulphone Do. 15"-.- l-amino-Z-cyanodnitrobenzene do Bluish-red. 16 do Z-aminonaphthalene-5-methylsulphone Do. 17 do 2aminonaphthalene-5-ethylsulphone Do. 18 1-amino-2,4-dinitrobenzene Z-aminonaphthalene-5-methylsulphone Bordeaux. 19 do 2-aminonaphthalene-5-ethylsulphone. Do. 20 1-amino-2,4-dinltro-6-chloroben- Z-aminonaphthalene-S-methylsulphone Do.

zene. do Z-aminonaphthalene-5-butylsulphone Do. 22..- 1-amino 2,S-dichlorMnitroben- 2-aminonaphthalene-5-ethylsulphone Red.

zene. 23. 1-amino-2-bron1o-4-nitrobenzene Z-aminonaphthalene 5-rnethylsulphone Do. --..do 2-amin0naphthalene-5ethylsulphone Do. 1-amino-2-chloro-t-nitrobenzene do D0. 26.. l-amin0-2,4dinitro-6-bromo-ben- 2-aminonaphthalene-5-methylsulphone Bordeaux.

zene. 27-.- I-aminO-ZG-dllJrOmOA-nitmben- .dn Red.

zene.

EXAMPLE 23 30 solution of 23.5 parts of 2-aminonaphthalene-4-ethylsu1- phone in 100 parts (36%) hydrochloric acid, 1000 parts of Water and 5 parts of a fatty alcohol-polyglycol ether. Thereupon the pH of the reaction mixture is adjusted to 4-4.5 with sodium acetate. The precipitated dyestufi' having the formula A slurry consisting of 17.3 parts of l-amino-Z-chloro- 4-nitro-benzene in 300 parts of water and 30 parts of hydrochloric acid (36%) is diazotized at 0-5 by the dropwise addition of 6.9 parts of sodium nitrite in 50 parts of water. The clear diazonium salt solution is added dropwise at 0-5 to a solution of 22.1 parts of Z-aminonaphthalene-S-methylsulphone in 100 parts acetic acid IIIHZ (80%), 20 parts hydrochloric acid (36%) and 1200 parts of water. After an hour the pH of the reaction mixture is adjusted to a value of 4-4.5. l

The red coupling product which precipitates in an easily N 02 SOz-CHa-CHB filterable form is filtered and washed with a lot of water; it corresponds to the formula:

1 is filtered and washed with a great deal of water, and dried 0 n vacuo at 60". A red powder is thus obtained. On grind- 1 mg, the dyestutf with an anion active dispersing agent 01 so CH this product dyes cellulose triacetate fibres in the presence 2 3 of such colour carriers as o-phenylphenol, in red shades which are fast to light and washing.

The coupling component used above is prepared, for example by reacting 2-acetylaminonaphthalene-4-sulphinic acid with diethyl sulphate and thereupon saponifying the acetylamino group.

If in the above example instead of the 13.8 parts 1- amino 2 nitrobenzene equimolecular amounts of the I diazo components listed in Table XI are reacted with the EXAMPLE 24 coupling components listed in column 3, under the con- The diazonium compound resulting from 13.8 parts of ditions as given above, dyestulfs are obtained having The red dyestuff is dried in vacuo at 60-70 whereupon it is ground with a synthetic dispersing agent. Polyester fibres such as Dacron can be dyed in red shades with an aqueous dispersion of the dyestuif, obtained as described above, possibly with the addition of colour carriers. The dyeings are very fast to washing, sublimation and light.

1-am1no-2-n1trobenzole 1s added dropwise at 05 to a similar dye qualities.

TABLE XI Shade on polyester No. Diazo component Coupling component or mixture of coupling components fibres 1....-- l-aminoa-nitrobenzene Z-amlnonaphthalene-4-p-tolylsnlnhnn Red. 2 do 2-aminonaphthalene-4-isopropylsnlnhnnn Do. a d n Z-aminonaphthalene-8-methylsnl hnne Scarlet. 4 l-ammo-Z-nitro--methylbenzene 2-aminonaphthalene-3ethylsulphone Dc. 5 l-amino-2-chloro-4-nitr0benzene- 2-aminonaphthalene-4-methylsulphone Red violet. 6 do 2-aminonaphthalene-3-ethylsulphone- Red. 7 l-amindZ-methoxy-4-nitrobenzene. Z-aminonaphthalene-4-pheny1sulphone- Red violet. 8 1-am1no-2-cyano4-nitrobenzene 2-aminonaphthalene-4-methylsulphone; 2-aminonaphthalene 4-ptolylsulphone Do. 9 do 2-aminonaphthalene-4-butylsnlnhmm Do. 10.- 1-amino-2 4-dimtrobenzene 2-aminonaphthalene-4-methylsulphonerd 11 d0 2-amlnonaphthalenei-ethylsulphone- D i 12"..- l-amlno-Z-bromo-4-nitrobenzene- 2-ammonaphthalene-t-methylsulphone; 2-aminonaphthalene-4-ethy1snlpl1one Red violet.

37 EXAMPLE 25 In a pressure dyeing apparatus, 3 parts of the dyestulf obtained according to Example 1 are finely dispersed in 2000 parts of water containing 5 parts of an anion active synthetic dispersing agent. The pH of the dye bath is adjusted to 6-6.5 with acetic acid.

100 parts of terephthalic acid polyglycol ester fabric are entered at 50, the bath is heated within 40 minutes to 130-135 and dyeing is performed for 1 hour at this temperature. The dyeing is rinsed with water and soaped. A red dyeing which is fast to perspiration, rubbing, sublimation and light is obtained.

The dyestuffs described in the other examples produce similarly good dyeings when the conditions above described are kept.

EXAMPLE 26 2 parts of the dyestuff obtained according to Example 3 are dispersed in 4000 parts of water. 12 parts of the sodium salt of o-phenylphenol and 12 parts of diammonium phosphate are added to this dispersion and 100 parts of a polyester fabric are dyed for 1 /2 hours at 95- 98". The dyeing is rinsed and after-treated with dilute caustic soda lye and a dispersing agent.

A bluish-red dyeing is obtained which is fast to washing, rubbing, light and sublimation.

If in this example, the 100 parts of terephthalic acid polyglycol ester fabric are replaced by 100 parts of cellulose triacetate fabric, dyeing is performed under the conditions given and the dyeing is then rinsed with water, then a bluish-red dyeing is produced which has very good fastness to perspiration, rubbing and sublimation.

EXAMPLE 27 Polyglycol terephthalate fabric such as Dacron is impregnated in a padding mangle at 40 with an aqueous dispersion composed as follows:

20 parts of the dyestulf obtained according to Example 4, finely dispersed in 7.5 parts of sodium alginate,

20 parts of triethanolamine,

20 parts of a non-ionogenic wetting agent and 900 parts of water.

The fabric is squeezed out to 100%; increase of its original weight, dried at 100 and the dye is fixed for 30 seconds at a temperature of 210. The dyed fabric is rinsed with water, soaped and dried. Under these conditions, a bluish red dyeing is obtained which is fast to washing, rubbing, light and sublimation.

The dyestuffs described in the other examples also produce dyeings of equal quality by this process.

EXAMPLE 28 1.5 parts of the dyestuff obtained according to No. 16 of Table IX are dispersed in 4000 parts of water. To the resulting dispersion there are added:

2 parts of the condensation product of coconut oil fatty acid, dicyanodiamide and p-anisidine (molar ratio 1:1:1) subsequently monosulfonated,

2 parts of the condensation product of Z-naphthalene sulfonic acid and formaldehyde (molar ratio about 1.75:1),

2 parts of ammonium sulfate, and

20 parts of the sodium salt of o-phenylphenol.

100 parts of polyglycol terephthalate fabric are introduced into this bath at 70 C.; the bath is heated up to 100 within 30 minutes and kept for 90 minutes at 100 C. The dyeing is then rinsed and after-treated with aqueous 2%-sodium hydroxide solution and a solution containing 2 grams per liter of p-nonylphenolhexaglycol ether.

Under these conditions, a bordeaux dyeing is obtained which is fast to light and sublimation.

38 We claim: 1. A non-metallizable monazo dyestuff free from sulfonic acid and carboxylic acid radicals, of the formula wherein A is a member which is linked via the -SO bridge to one of the positions 3, 4, 5, 6, 7 and 8 of the naphthalene nucleus, and is selected from the group consisting of (a) the amino group;

(b) a mono-substituted amino group, wherein the substituent is one of the following: alkyl with from 1 to 10 carbon atoms, hydroxy-lower alkyl, lower alkoxy-lower alkyl, lower alkanoyloxy-lower alkyl;

(c) a disubstituted amino group wherein each substituent is one of the following: alkyl with from 1 to 10 carbon atoms, hydroxy-lower alkyl, lower alkoxy-lower alkyl, lower alkanoyloxy-lower alkyl;

(d) a substituted amino group wherein one of the amino nitrogen bonds is occupied by one of the following: hydrogen, alkyl with from 1 to 10 carbon atoms, hydroxy-lower alkyl, lower alkoxy-lower alkyl, lower alkanoyloxy-lower alkyl, and another amino nitrogen bond is occupied by one of the following: benzoyloxy-lower alkyl, cycloalkyl with six ring carbon atoms, benzyl, phenyl, lower alkylphenyl, lower alkoxy-phenyl, chlorophenyl, bromophenyl;

(e) phenoxy;

(f) lower alkyl-phenoxy,

(g) phenyl-phenoxy,

(h) lower alkoxy-phenoxy,

(i) hydroxy-lower alkoxy-phenoxy,

(j) phenoxy-phenoxy,

(k) lower alkoxy-carbonyl-phenoxy,

(l) carbamyl-phenoxy,

(m) N-carbamylphenoxy substituted at the nitrogen atom with from one to two of the following substituents: lower alkyl, hydroxy-lower alkyl, lower alkoxy-lower alkyl;

(n) N,N-di-(lower alkyl)-amino-phenoxy,

(0) lower alkanoyl-amino-phenoxy,

(p) chloro-phenoxy,

(q) bromo-phenoxy;

(r) naphthyl-(1)-oxy,

(s) naphthyl-(2)-oxy;

( Py y y;

(u) morpholinyl-(l) and p p y and wherein B is a benzene radical substituted by from one to three members selected from the group consisting of chlorine, bromine, nitro, cyano, methyl, methoxy, trifiuoromethyl, carboethoxy and carbobutoxy, at least one of which members is nitro or cyano.

2. A dyestufl" as defined in claim 1, wherein the grouping A 40 is linked to the 4-, 5- or 6-position of the naphthalene nucleus.

3. A dyestufi as defined in claim 1, wherein the grouping A SO is linked to one of the positions 5 and 6 of the naphthalene nucleus and wherein B is of the formula 40 wherein Y is selected from among hydrogen, chlorine, 7. A monoazo dyestuif as defined in claim 3, which is bromine, a nitro and cyano, nitro and Z is selected from of the formula among hydrogen, chlorine and bromine.

4. A monoazo dyestuif as defined in claim 3, which is N112 of the formula I CN --SOzNHCH; 10 001i;

8. A monoazo dyestuff as defined in claim 3, which is of the formula 5. A monoazo dyestulf as defined in claim 3, which is of the formula 1 I I Cl References Cited 402N112 UNITED STATES PATENTS 2,776,956 1/1957 Zickendraht et al. 260196X 6. A monoazo dyestuff as defined in claim 3, which is 25 2839520 6/1958 Neler' of the formula FOREIGN PATENTS 512,378 12/1952 Belgium 260196 IIIH2 FLOYD D. HIGEL, Primary Examiner 02N N=N 30 l US. Cl. X.R. ON SO2NH 

